Production of colored photographic images with oxodiazole couplers



Unite States Patent Ofi ice 2,897,079 Patented July 28, 1959 PRODUCTION OF COLORED PHOTOGRAPHIC MAGES WITH OXGDIAZOLE COUPLERS No Drawing. Application March 21, 1957 Serial No. 647,473

Claims priority, application Great Britain March 23, 1956 p 6 Claims. (Cl. 96-55) The present invention relates to a process for the manufacture of colored photographic images by color development in the presence of a color coupler, to photographic developers or to photographic material which contain such color coupler, and to photographic images obtained according to this process.

It is known to obtain a colored photographic image by developing a reducible silver salt image in the presence of a color coupler, i.e. a compound which during development couples with the oxidation product of the developing agent and forms adyestufr' which precipitates onto the developed silver grains.

Magenta colored images are usually obtained by development in the presence of compounds which contain an active methylene group, for example compounds whereinthe methylene group is connected at one side with a heterocyclic ring and at the other side with another group capable of activating a methylene group such as a cyan group. Such compounds are for instance oxodiazolyl-Z-acetonitrile and cyano-acetyl coumarone. Now we have found a class of compounds suited for use as color coupler, some members of which supersede the known compounds by showing higher reactivity, yielding dyes with smaller and more sharply limited absorption curves (which means more saturated colors), and yielding perfectly transparent images.

It is an object of the present invention to provide a new process for the production of colored photographic images by color development.

Another object of this invention is to provide new photographic developers containing a color coupler.

A further obqect is to provide new photographic material containing a color coupler.

Still further objects will become apparent from the following description.

According to the present invention, a reducible silver salt image is developed with an aromatic amino developing agent in the presence of a compound according to the formula obtained by reaction of HONH with nitriles (RSO CH --CN). The latter are obtained by reaction of chloro-acetonitrile with the sodium salts of sulphinic acids (RSO H).

The preparation of nitriles with various radicals R is described by I. Troger and W. Hille: J. Pr. Chem. (2),

71- (1905), 225-236, and the preparation of the corresponding amidoximes by J. Troger and P. Volkmer, loc. cit., pages 236-248.

The presence of color couplers according to the present invention during color development may arise from adding to the photographic material or to the developer, a compound which differs from the color coupler only because in the active CH -group one or two hydrogen atoms are replaced by a group splitting oif either before development occurs by the action of the alkali in the developing solution or during the color development.

The color couplers of the present invention may be added to the developer or to a colloid layer, either to a light-sensitive silver halide emulsion layer or to a nonlight-sensitive layer, adjacent to a sensitive layer or separated therefrom by a permeable colloid layer. They are, however, particularly suited for use in -the developer as illustrated hereinafter.

The aromatic amino compounds, which according to the present invention are used as developing agents, com-- prise mono-, diand tri-amino aryl compounds, particularly N:N-dialkyl-para-phenylene diamines and derivatives such as N:N-dialkyl-N-sulphoor carboxy-methylpara-phenylene diamines.

The following examples serve to illustrate the present inventionwithout limiting, however, the scope thereof.

EXAMPLE 1 22.8 g. (0.1 mol) p-tolusulphonyl-acetamidoxime obtained by the method described by J. Troger and P. Volkmer (loc. cit.) are suspended in 250 cm. anhydrous benzene. Whilst heating, 20.7 g. (0.2 mol) cyanoacetyl chloride are addded within 15 minutes. Next, part of the benzene (about 150 cm?) is distilled off. After cooling, the precipitate is separated by filtration and refluxed for 15 minutes in 150 cm. acetic acid. The reaction mixture is poured out into 1 litre water. The precipitate is sucked off and recrystallized from methanol and benzene respectively. A product, melting at 127 C. and corresponding to the Formula I wherein R=ptolyl, is obtained.

An exposed photographic film strip, coated with a A silver halied emulsion layer, is developed in a bath of the following composition:

Solution A G. (NaPO .I. 1 Na SO (anhydrous) 3 N:N-diethyl-p-phenylene-diamine hydrochloride 3 Na SO (anhydrous) 40 Na- CO (anhydrous) 35 KBr 1.5 Water to 900 cm.

Solution B NaOH 1.5 3-(p-tolylsulphonyl-methyl) 5 cyanomethyl-oxodiazol-1:2:4 1

Water to 50 cm.

Before use, solution B is added to solution A and water developed image is rinsed for 30 minutes an the silver is bleached in the following bath:

G. K Fe(CN) KBr 3 Water to 1000 cm.

The image is rinsed again for 10 minutes and then fixed Y and again rinsed for 30' minutes.

EXAMPLE 2 Beta-naphthyl-sulphonyl-acetarnidoxirne, melting at 143 C., is prepared as described by J. Troger and P. Volkmer (loc. cit.). 26.4 g. (0.1 mol) of this amidoxime are treated with 15 g. (0.15 mol) cyanoacetyl chloride in ethereal solution. After heating for 2 /2 hours on the waterbath, the precipitate is filtered off, Washed with an aqueous solution of H SO N and next with water until neutral reaction of the wash water, boiled in a minimum of acetic acid and poured into water. A color coupler, corresponding to Formula I, wherein R beta-naphthyl, and melting at 122124 C., is obtained.

By exposing and further treating a film strip as in Example 1, but replacing the color coupler by that described in the present example, a magenta image with an absorption maximum at 525 m is obtained.

EXAMPLE 3 p-Nitrophenyl-sulphonyl-acetonitrile melting at 159 160 C. and the corresponding amidoxime melting at 195 196 C. are prepared by the same method as described by J. Troger and P. Volkrner (loc. cit.) for beta-naphthylsulphonyl-aceto-amidoxime.

25.9 g. (0.1 mol) amidoxime of p-nitrophenyl-sulphonyl-aceto-nitrile are treated in anhydrous ether with 15 g. (0.15 mol) cyano acetyl chloride. The pricipitate is sucked off, boiled in acetic acid, poured intp water and recrystallized from methanol. A color coupler corresponding to Formula I, wherein R=p-nitrophenyl, and melting at 205207 C., is obtained.

By exposing and further treating a film strip as in Example 1, but replacing the color coupler by that described in the present example, a magenta image with an absorption maximum at 518 m is obtained.

EXAMPLE 4 by nitration of p-tolylsulphonyl-acetonitrile and melting 'at 115-116 C. is transformed into the corresponding amidoxime melting at 152 C. by the method of I. Troger and P. Volkmer (c. cit.). A mixture of 27.3 g. (0.1 mol) of this amidoxirne, suspended in 200 cm. anhydrous ether, and g. (0.15 mol) cyano-acetyl chloride are refluxed for 9 hours on the water bath. The precipitate is filtered off, washed with an aqueous solution of H SO N and with water, boiled in acetic acid and poured into Water. After recrystallization from a mixture of water and acetone, a color coupler corresponding to Formula I, wherein R:3-nitro-4methylphenyl, and melting at 149-150 C. is obtained.

By exposing and further treating as in Example 1, but replacing the color coupler by that described in the present example, a magenta image with an absorption maximum at 515 111,11. is obtained.

EXAMPLE 5 Chloroacetonitrile is added under reflux and in 100% excess to 60 g. of the magnesium salt of butyl sulphinic. acid (CH -(CH -SO Mg.2H O, prepared according to the method of G. l-ioulton and H. V. Tartar: J. Amer. Chem. Soc., 60 (1938), 544-51, and suspended in 250 cm. (CH N.CHO. A perfect solution is obtained which is refluxed for 1 hour. A little pricipitate is sucked off. The precipitate, obtained by diluting the filtrate with Water, is extracted with ether. The extract is dried and distilled in circumstances such as 138140 C./ 0.4 mm. and 148150 C./0.6 mm. A pale yellow oil having the formula CH (CH SO CH CN and solidifying after a long time is obtained. Melting point: 3739 C.

Analysis.N calculated 8.70%; found 8.728.6%. S calculated 19.86%; found 20.0320.24%.

9 g. of this product are dissolved in 150 cm. C H OH A and a solution of 5.8 g. NH OHHCI, and 4.5 g. Na CO in 75 cm. water are added. The whole is refluxed for 45 minutes and filtered while warm on bone black. The precipitate formed after cooling is sucked off and recrystallized from a mixture of equal volumes of C H OH and benzene. A product melting at 121 C. and corresponding to the formula N OH is obtained.

10 g. of this amidoxime in benzene are kept with distilled cyanoacetyl chloride in 50% excess for 30 minutes at room temperature and for 1 hour at C. The separated precipitate is boiled with CH COOH, recrystallized twice from a mixture of equal volumes of Water and CH COOH. A product melting at 102104 C. and corresponding to Formula I, wherein R=CH (CH is obtained.

By exposing and further treating as in Example 1, but replacing the color coupler by that described in the present example, a magenta image with an absorption at 510 m, is obtained.

EXAMPLE 6 The developing solution given in Example 1 may be replaced by the following:

Before use, solution B is added to solution A and water is added to the resulting solution to 1000 9 111.

By the use in this solution of the derivative, wherein R=p-totyl, as color coupler and as color developing sub stance of 1-(beta-methylsulphonamido-ethyl)-6-aminotetrahydroquinoleine, 1 (delta sulphobutylene) 5 6- amino-tetrahydroquinoleine, or 9-amino-julolidine, images with an absorption maximum at 535, 580, 540-545 mg respectively are obtained.

We claim:

1. A process for the production of a colored photographic image, which comprises developing a reducible silver salt image in a photographic element by means of a primary aromatic amino developing agent in the presence of a color coupler having the following formula:

wherein R represents a member selected from the group consisting of an alkyl radical and an aryl radical.

2. A process for the production of a colored photographic image, which comprises developing a reducible silver salt image in a photographic element by means of a primary aromatic amino developing agent in the presence of a color coupler having the following formula:

t RSOzCH:O C-CH -CN wherein R=ary1.

3. Photographic developer containing a primary arowherein R represents a member selected from the group consisting of an alkyl radical and an aryl radical.

4. Photographic developer containing a primary aromatic amino developing agent and a color coupler having the following formula:

5. A photographic material comprising at least one silver halide emulsion layer, one of the layers containign a color coupler having the following formula:

wherein R represents a member selected from the group consisting of an alkyl radical and an aryl radical.

6. A photographic material comprising at least one silver halide emulsion layer and at least one other colloid layer, one of said layers containing a color coupler having the following formula:

wherein R= aryl.

References Cited in the file of this patent UNITED STATES PATENTS 2,380,809 Verkinderen et al July 31, 1945 FOREIGN PATENTS 638,039 Great Britain May 31, 1950 

1. A PROCESS FOR THE PRODUCTION OF A COLORED PHOTOGRAPHIC IMAGE, WHICH COMPRISES DEVELOPING A REDUCIBLE SILVER SALT IMAGE IN A PHOTOGRAPHIC ELEMENT BY MEANS OF A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF A COLOR COUPLER HAVING THE FOLLOWING FORMULA: 